Film forming and mechanical lubricant combination

ABSTRACT

An environmentally friendly lubricant composition useful for well contains: between 40% and 80% by volume of unsaturated fatty acid(s) having between 16 and 26 carbon atoms and between one and three carboxylic acid moieties, or triglyceride(s) having from 16 to 26 carbon atoms and at least one double bond, or mixture thereof;  
     at least about 20% by weight of a suspension agent which is a Group I and/or Group II metal salt or base that is reactable with a carboxylic acid moiety in the unsaturated fatty acid; a film-forming amine R 1 —N—(R) 2  wherein the amine has between ten and thirty carbon atoms; or mixtures thereof, wherein the amount of suspension agent is sufficient to provide at least a 50% overbased composition; and between about 10 and about 50 pounds of a polymeric beads per barrel of lubricant composition, wherein said lubricant composition is blended to form a substantially homogenous composition.

RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application60/451,871 filed Mar. 4, 2003, the disclosure of which is incorporatedherein for all purposes.

FIELD OF THE INVENTION

The present invention relates to lubricants having a film-formingcomponent, a suspension agent, and a mechanical lubricant, and use ofthe lubricants for example in oilfield applications including use indrilling fluids workover and completion fluids.

BACKGROUND OF THE INVENTION

Lubricant compositions are materials that can be introduced betweenopposed solid surfaces, e.g. the surfaces of machine parts, in order toprevent these surfaces from contacting each other and to facilitate anyrelative motion between them as far as necessary. As a consequence, suchlubricant compositions normally need to have hydrodynamic properties,i.e. the capacity of building up an internal pressure which issufficient to balance the load on the opposed surfaces, and furtherfriction-reducing and wear-reducing properties.

Many lubricant compositions have the form of oils and greases and can beused for a wide variety of applications. Lubricant oils may be based onpetroleum derivatives, animal or vegetable oils or on syntheticmaterials such as polyalkylene glycols, dibasic esters, phosphateesters, silicones, silicate esters and the like. Lubricant greases arecombinations of such oils with thickening agents such as e.g. metalsoaps, modified clays, fine silicas and the like, and/or fillers such ase.g. asbestos, graphite, metal carbonates, hydroxides, oxides,phosphates, sulfides and the like. Moreover, lubricant oils and greasesmay contain special additives, e.g. to resist oxidation and corrosionand to improve such properties as adhesion, film strength and resistanceto water wash out.

Lubricants of the type described herein at particular useful whenincorporated with or used in conjunction with drilling muds or fluids.U.S. Pat. No. 4,230,586 relates to aqueous well-drilling fluidscontaining additives comprising colloidal disperse systems andemulsifiers. Such additives provide lubricity to the drilling fluids andthus allow rotary drilling operations to be carried out at reducedtorque and drag (vertical movement). Methods of carrying out drillingoperations using these drilling fluids are also within the scope of thisreference. U.S. Pat. No. 4,301,016 provides a method for drilling aborehole wherein a drilling fluid comprises an aqueous composition whichcontains an effective amount of an emulsion polymerized latex comprisedof an interpolymer of an olefinically unsaturated carboxylic acidmonomer and at least one other, non-carboxylated polymerizable monomer.

The primary functions of a drilling fluid mud are: to carry chips andcuttings produced by drilling to the surface; to lubricate and cool thedrill bit and drill string; to form a filter cake which obstructsfiltrate invasion in the formation; to maintain the walls of theborehole; to control formation pressures and prevent lost returns; tosuspend cuttings during rig shutdowns; and to protect the formation forlater successful completion and shutdown. Drilling muds or fluid in oilwells are normally pumped continuously down the drill stem, throughapertures in the drill bit and are then forced up to the surface throughthe annular space between the drill stem and the side of the hole,carrying the rock cuttings in suspension. At the surface the cuttingsare separated from the drilling mud and the latter is then recycled.Prior to cementing the mud is replaced by a Spacer Fluid whichtransports loose particles from the hole and leaves a clean, water-wetsurface to provide a good cement bond.

Certain rocks cause particular problems during drilling or excavation,due to their tendency to disintegrate in the drilling fluid to formfines which are very difficult to separate from the fluid and rapidlybuild up in the recycle stream causing increasing viscosity. Chief amongthe problem rocks is shale which generally disintegrates in the presenceof water. An acceptable drilling fluid or mud needs to have a viscositywhich is sufficiently low under conditions of shear to flow readily, butit also has to possess solid suspending properties. To achieve theseconflicting requirements a thixotropic fluid is usually required.Moreover it must not cause excessive breakdown of rocks such as shale.If it is to be useful for deep drilling, the fluid must be thermallystable, and it is important that excessive loss of fluid into theformation should be avoided. These requirements have been achieved byusing either oil or an oil-in-water emulsion as the drilling fluid. Theoil coats particles of shale and protects them from contact with water,thereby inhibiting their disintegration. However this in turn creates anenvironmental problem, especially in offshore drilling operations, whenthe rock cuttings are discarded. To avoid serious pollution the oil mustbe cleaned from the cuttings, before they can be dumped. It is difficultand expensive to reduce the oil contamination to currently permittedlevels, but even these small amounts of residual oil are ecologicallyundesirable, and there is pressure to replace oil based drilling fluidsaltogether. Oil-based muds/fluids also give rise to a fire hazard.

Prior art oil-based drilling muds and lubricants have contained minorproportions of surfactants as emulsifying agents for the oil or asdispersants for sludge. The surfactants have typically been presentessentially as monolayers surrounding colloidal size droplets orparticles of oil or dispersed solid. The protection of shale in drillingmuds has been essentially due to the shale being coated with oil. Thesuspending properties and thixotropic character of oil based drillingmud has been provided by the interaction of the dispersed oil droplets.

However environmental pressure is increasingly compelling drillingcompanies to adopt water based fluids in place of oil based muds. Anaqueous solutions containing polymeric suspending agents or dispersantsand/or bentonite to suspend the rock cuttings is less environmentallyharmful, and may be somewhat cheaper than the use of oil based muds. Thesolid suspending properties are provided by polymeric thickeners such assodium carboxymethyl cellulose or methacrylates. In the case ofwater-based muds, the protection of the shale has been provided by thepresence of polymers which encapsulate the shale particles irreversiblyand are therefore consumed quantitatively when the rock is drilled. Fordeep drilling or for drilling through shale, such aqueous fluids areoften inadequate. They have insufficient thermal stability to withstandthe high temperatures of deep formations and they can cause breakdown ofthe shale. Their lubricity is also generally inferior to that of oilbased muds. Attempts have been made to improve the performance ofaqueous drilling fluids with a variety of special additives such aspolymeric coating agents, and high concentrations of electrolyte to helpstabilize shale. These have not succeeded in providing an aqueous fluidwith adequate performance to replace oil based muds for deep drilling.

Solid particle lubricant compositions, which have particulate solids,are used in cases where the opposed surfaces are subjected to extremepressures and work loads during use. Such particulate solid lubricantsmay consist of inorganic compounds having laminar crystal lattices suchas crystalline graphite, molybdenum disulphide and the like, other softinorganic compounds such as lead oxide, lime, talc, bentonite and thelike, soft organic compounds such as soaps, waxes and fats, softpolymers such as poly(tetrafluoroethylene) or poly(chlorofluoroethylene)and the like, or malleable metals such as aluminium, copper, lead andthe like, or fracturable metals such as zinc. These solid lubricantsolids are elastic, malleable or fracturable, and they are generallysoft in the particular sense of having rather low yield limits to theirmechanical properties. The particulate solid lubricants may be used assuch or as dispersions in oils, even water-based vehicles.

U.S. Pat. No. 4,280,915 describes a base drilling fluid which hasenhanced lubricating properties in the presence of polyvalent cationscomprising a mixture of (1) water; (2) finely divided inorganic solids;(3) an alkanolamide of a saturated fatty acid having 8 to 20 carbonatoms, or triglycerides thereof, and (4) an alkanolamide of anunsaturated fatty acid having 18 carbon atoms, or triglycerides thereof.The alkanol amide is a reaction product of a mono- or di-substitutedamines having C1-C10 range mono- and di-alkanol substituents, and areactant selected from the group consisting of C8-C20 range saturatedfatty acids or triglycerides wherein at least 50% of the fatty acids aresaturated. The unsaturated fatty acid, however, should not be reactedwith excess amounts of alkanolamine. U.S. Pat. No. 5,007,489 suggestsdrilling lubricants comprising a system, one component of which is anamine sulfonate prepared from a half ammonium, half isopropylamine saltof the sulfosuccinic acid ester of the oleic acid amid of isopropanolamine.

U.S. Pat. No. 5,348,938 teaches adding oleophilic basic amine compoundsto drilling fluid in amounts of up to about 10 lb/bbl.

U.S. Pat. No. 4,715,971 provides a well drilling and completioncomposition having a potassium salt of a copolymer of a first compoundwith a formula CH₂═CR₁—COOH wherein R₁ is selected from the groupconsisting of H, and an alkyl having 1 to 4 carbon atoms, and a secondcompound having a formula CH₂═CH—COOR₂ wherein R₂ is selected from thegroup consisting of an alkyl radical and a hydroxyalkyl radical whereinthe alkyl and hydroxy each have 1 to 4 carbon atoms. The well drillingand completion composition of this invention also has an acceleratorcatalyst which includes water, KOH, lignite, sulfonated polystyrene, anda vinylsulfonate/vinylamide copolymer if the temperature of the systemis above 285° F.

U.S. Pat. No. 5,223,163 is directed to improved viscosity propertiesresulting from highly alkaline low viscosity overbased phenatescomprising the overbased reaction product of a source of alkylatedphenol, and a source of an alkali or alkaline earth metal containingreagent which is overbased in the presence of a dispersant compositionand a carboxylic acid or its derivative.

The use of polymeric beads as a lubricant or a fluid loss additive indrilling mud is known. U.S. Pat. Nos. 4,063,603; 4,172,031; 4,269,279;4,384,095 and 4,427,793 describe beads of one or more crosslinkedpolymers, e.g., polymers of styrenes, PVC/vinylacetate, vinylidenechloride/acrylonitrile, methylmethacrylate and ethylacrylate, andstyrene and divinylbenzene copolymers, that are useful in a drillingenvironment. U.S. Pat. No. 4,063,603 describes using beads as alubricant, wherein the beads are further aided by other lubricants,e.g., vegetable oils, such that the beads are suspended in vegetable oiland circulated in the well bore mixed with the drilling mud.

U.S. Pat. No. 5,792,727 describes lubricant compositions such asdrilling muds and high pressure lubricants, which can be used forapplications where extreme pressures and work loads are involved. Thelubricant compositions are dispersions of solid particles in asupporting vehicle. The solid particles are substantially sphericalparticles of a hard, abrasion-resistant and fracture-resistant,thermally stable and chemically inert material. This patent teaches thatsuitable particles are made primarily of ceramic materials, althoughsome materials of other nature may also be appropriate, particularlysilica-based materials. Examples include particles of silica-aluminaceramics, optionally including oxides of other materials, and fusedsilica. This patent teaches that glass beads having a hardness of 5.5 onthe Moh's scale are generally unsuitable since they have a lowcompressive strength, a softening point of about 730° C. and they aresusceptible to attack by alkali. The solid particles are incorporated ina supporting vehicle which may be any petroleum-based, organic-based,silicone-based or even water-based vehicle, preferably lubricant oilsand greases. The lubricant greases to be used as a supporting vehiclewill normally be a combination of such oils with thickening agents, suchas e.g. metal soaps (salts of alkaline or alkaline earth metals withmonobasic or polybasic aliphatic acids, such as sodium, lithium, bariumstearates, hydroxystearates, oxalates, sebacates and the like), modifiedclays, fine silicas and the like, and/or fillers or additives such ase.g. asbestos, graphite, metal carbonates, oxides, hydroxides,phosphates, sulphates, sulfides, and the like. Such thickening agents,fillers and additives are normally used in gelled form or in fineparticulate form, as appropriate. The lubricant composition maypreferably comprise about 50 to 60% by weight of particles of a hard,abrasion-resistant and fracture-resistant, thermally stable andchemically inert material, and about 40 to 50% by weight of a lubricantoil or lubricant grease.

U.S. Pat. No. 5,700,767 describes a downhole well lubricant having theproperties of coating metal surfaces submerged in a water based wellliquid and, in response to friction between the coated metal surfacessubmerged in the water based well liquid, producing a greasy water basedemulsion on the metal surfaces, the lubricant consisting essentially of20-70 pounds per barrel of a stearate surfactant; and a liquid componentbeing 20-50% of a filming amine; 20-80% of an activator selected fromthe group consisting of petroleum solvent comprising a mixture of C7-C10saturated hydrocarbons, 1,2,4 trimethylbenzene and C8+aromatics; coconutoil; terpene; xylene; toluene; benzene; mineral oil; turpentine; andmixtures thereof, and balance diluent

U.S. Pat. No. 5,851,961 describes an anti-settling lubricity agent forwater/oil dispersions comprising a mixture of: water;

A) an overbased non-Newtonian colloidal mixture of solidmetal-containing colloidal particles, e.g., alkali or alkaline earthmetal acetates, formates, carbonates, sulfides, sulfites, thiosulfides,and halides, predispersed in a dispersion medium of at least one inertorganic liquid and at least one organic compound having polarsubstituents and hydrophobic portions which is substantially soluble inthe disperse medium;

(B) a water soluble associative thickener comprising a base-neutralizedcarboxlated copolymer of a carboxyl-containing, ethylenicallyunsaturated hydrocarbon and a nonionic surfactant acrylate; and

(C) at least one carboxylic acid is selected from the group consistingof tall oil fatty acids, linoleic acid, abietic acid, linolenic acid,palmitoleic acid, oleic acid and ricinoleic acid.

What is needed is lubricant compositions containing environmentallybenign components, where the composition is useful at deep pressures butwhich advantageously has substantially no inorganic solid material.

SUMMARY OF THE INVENTION

In a first embodiment, the inention is a lubricant compositioncomprising:

A) between about 40% and about 80% by volume of a film forming lubricantconsisting essentially of unsaturated fatty acid(s) having between about16 and about 26 carbon atoms and between one and three carboxylic acidmoieties, or triglyceride(s) having from about 16 to about 26 carbonatoms and at least one double bond, or mixture thereof;

B) at least about 20% by weight of a suspension agent comprising:

-   -   1) a metal compound reactable with at least one carboxylic acid        moiety in the unsaturated fatty acid, wherein the metal is a        Group I metal, a Group II metal, or mixture thereof;    -   2) a film-forming amine R₁—N—(R)₂, where:        -   a) each R is independently an H or a C₂ to C₅ alkylene, and            R₁ is a C₃ to C₂₄ saturated or unsaturated aliphatic group            or two saturated or unsaturated aliphatic groups with an            oxygen therebetween, wherein the amine has between ten and            thirty carbon atoms;        -   b) each R is independently an H, a C₂ to C₅ alkylene, or a            C₁ to C₅ alkyl or alkanol, and R₁ contains between 10 and 24            carbon atoms and is a C₁₀ to C24 mono- or poly-unsaturated            hydrocarbon radical or a group R₂—O—R₃; wherein R₂ and R₃            are hydrocarbon moieties and at least one of R₂ and R₃ is a            mono or poly-unsaturated hydrocarbon radical; or        -   c) mixtures thereof, wherein the amount of suspension agent            is sufficient to provide at least a 50% overbased            composition; and

C) between about 10 and about 50 pounds of a polymeric particulate thatfunctions as a mechanical lubricant per barrel of lubricant composition,wherein said lubricant composition is blended to form a substantiallyhomogenous composition.

In an alternate embodiment, the lubricant composition comprises:

between about 50% and about 75% by volume of tall oil fatty acids;

between 20% and about 45% by weight of the suspension agent; and

between about 10 and about 35 pounds of the polymeric particulate thatfunctions as a mechanical lubricant per barrel of lubricant composition.

In another alternate embodiment, the lubricant composition consistsessentially of:

between about 50% and 80% by volume of tall oil fatty acids;

between 20% and about 45% by weight of the suspension agent, wherein thesuspension agent comprises the metal compound, and wherein the metal isa Group I metal, a Group II metal, or mixture thereof; and

between about 10 and about 35 pounds of the polymeric particulate thatfunctions as a mechanical lubricant per barrel of lubricant composition.

In another alternate embodiment, the lubricant composition comprises:

between about 60% and about 70% by volume of unsaturated fatty acid(s)having between about 18 and about 22 carbon atoms and between one andthree carboxylic acid moieties;

between 30% and about 40% by weight of the suspension agent, wherein thesuspension agent comprises the metal compound, and wherein the metal isa Group I metal, a Group II metal, or mixture thereof; and

between about 15 and about 20 pounds of the polymeric particulate thatfunctions as a mechanical lubricant per barrel of lubricant composition.

In another alternate embodiment, the lubricant composition comprises:

between about 60% and about 70% by volume of tall oil fatty acids;

between 30% and about 40% by weight of the suspension agent, wherein thesuspension agent comprises a metal base compound, and wherein the metalis a Group I metal, a Group II metal, or mixture thereof; and

between about 15 and about 20 pounds of a polymeric particulate thatfunctions as a mechanical lubricant per barrel of lubricant composition.

In another alternate embodiment, the lubricant composition comprises:

between about 60% and about 70% by volume of the unsaturated fattyacid(s) having between about 16 and about 26 carbon atoms and betweenone and three carboxylic acid moieties, the triglyceride(s) having fromabout 16 to about 26 carbon atoms and at least one double bond, ormixture thereof;

between 30% and about 40% by weight of the suspension agent, wherein thesuspension agent comprises the metal compound, and wherein the metal isa Group I metal, a Group II metal, or mixture thereof; and

between about 10 and about 35 pounds of a polymeric particulate thatfunctions as a mechanical lubricant per barrel of lubricant composition.

In another alternate embodiment, the lubricant composition consistsessentially of:

between about 60% and about 75% by volume of the unsaturated fattyacid(s) having between about 18 and about 22 carbon atoms and betweenone and three carboxylic acid moieties;

between 30% and about 40% by weight of the suspension agent, wherein thesuspension agent comprises the metal compound, and wherein the metal isa Group I metal, a Group II metal, or mixture thereof; and

between about 15 and about 20 pounds of the polymeric particulate thatfunctions as a mechanical lubricant per barrel of lubricant composition.

In any of the above embodiments, the film forming lubricant may compriseat least 50% by weight of one or more tall oil fatty acids.

In any of the above embodiments, the suspension agent may consistessentially of a metal salt, wherein the metal is sodium, potassium, andlithium, magnesium, calcium, barium, or mixture thereof.

In any of the above embodiments, the metal ratio is beneficially betweenabout 2 and 12.

In any of the above embodiments, the polymeric particulateadvantageously consist of polymeric beads having a size between 40 meshto 100 mesh, wherein the beads comprise a cross-linked polymer orcopolymer of styrene, divinylbenzene, PVC/vinylacetate, vinylidenechloride/acrylonitrile, methylmethacrylate/ethylacrylate, orstyrene/divinylbenzene.

In any of the above embodiments, the polymeric particulateadvantageously consists of polymeric beads having a size between 60 meshto 80 mesh, the beads comprising a cross-linked polymerized divinylbenzene, styrene, divinyl benzene/styrene, polystyrene crosslinked withdivinyl benzene, or mixtures or combinations thereof.

In any of the above embodiments, the polymeric particulateadvantageously consists of polymeric beads having a weight averageparticle diameter between about 220 and about 280 microns, with lessthan 30% by weight having a diameter less than 150 microns and less than5% by weight having a diameter greater than about 350 microns.

In any of the above embodiments, advantageously the lubricantcomposition comprises less than about 2% by weight of each of: promotersuseful for forming the overbased film forming lubricant/suspension agentcomposition; resin acids; unsaponifiables; and saturated fatty acids andtheir isomers. Preferably, the lubricant composition comprises less thanabout 5% by weight total of promoters useful for forming the overbasedfilm forming lubricant/suspension agent composition, resin acids,unsaponifiables, and saturated fatty acids.

In any of the above embodiments, advantageously the lubricantcomposition comprises less than about 1% by weight of each of: promotersuseful for forming the overbased film forming lubricant/suspension agentcomposition; resin acids; unsaponifiables; and saturated fatty acids andtheir isomers.

In any of the above embodiments, advantageously the lubricantcomposition further comprises between about 0.1% and about 5%, ofinorganic particulate lubricant, for example, beads or particles ofgraphite, molybdenum disulphide, lead oxide, aluminum, copper, lead,zinc, glass, or ceramic. Preferably, the inorganic particulate lubricantcomprises or consists essentially of graphite, molybdenum disulphide,glass, or ceramic.

In any of the above embodiments, advantageously the film forminglubricant comprises at least 50% by weight of unsaturated fatty acidshaving between 18 and about 20 carbon atoms.

In any of the above embodiments, advantageously the lubricantcomposition is substantially free of aromatics, cadmium, and lead, e.g.,contains less than 500 ppm of each, preferably less than 100 ppm ofeach.

In any of the above embodiments, advantageously at least half of theequivalents of the suspension agent are salts or bases of Group IImetals. Alternatively, at least half by weight of suspension agent is analkaline earth metal base where the counter-ion is a hydroxyl, acarbonyl, a carbonate, or mixture thereof.

The above-described lubricants are particularly useful in treating wellsduring drilling or work-over operations including for example runningcoiled tubing. The method of lubricating a pipe in a wellbore comprises:

adding between about 0.2% and about 5%, preferably 0.5% to 4%, or 2-3%by volume of the lubricant composition of claim 1 to a treating fluid;and

circulating the fluid containing the lubricant into the well to placethe lubricant at the desired depth.

The treating fluid can be an aqueous-based drilling mud or an oil-baseddrilling mud, as well as simply oil or brine, or any combinationthereof.. The treatment amount is preferably about 2% and about 3% byvolume.

In a preferred embodiment, the lubricant composition comprises:

between about 50% and about 80% by volume of a film forming lubricantconsisting essentially of unsaturated fatty acid(s) having between about18 and about 24 carbon atoms and between one and three carboxylic acidmoieties;

between 20% and about 45% by weight of a suspension agent comprising ametal salt or metal base reactable with at least one carboxylic acidmoiety in the unsaturated fatty acid, wherein the metal is a Group Imetal, a Group II metal, or mixture thereof, wherein the amount ofsuspension agent is sufficient to provide at least a 50% overbasedcomposition; and

between about 10 and about 35 pounds of a polymeric particulate thatfunctions as a mechanical lubricant per barrel of lubricant composition,wherein the polymeric particulate consists of polymeric beads having asize between 40 mesh to 100 mesh, the beads comprising a cross-linkedpolymer or copolymer of styrene, divinylbenzene, PVC/vinylacetate,vinylidene chloride/acrylonitrile, methylmethacrylate/ethylacrylate, orstyrene/divinylbenzene; wherein said lubricant composition is blended toform a substantially homogenous composition.

This preferred lubricant may further comprise between 5% and 20% byweight of a film-forming amine R₁—N—(R)₂, where:

each R is independently an H or a C₂ to C₅ alkylene, and R₁ is a C₃ toC₂₄ saturated or unsaturated aliphatic group or two saturated orunsaturated aliphatic groups with an oxygen therebetween, wherein theamine has between ten and thirty carbon atoms;

each R is independently an H, a C₂ to C₅ alkylene, or a C₁ to C₅ alkylor alkanol, and R₁ contains between 10 and 24 carbon atoms and is a C₁₀to C₂₄ mono- or poly-unsaturated hydrocarbon radical or a group R₂—O—R₃;wherein R₂ and R₃ are hydrocarbon moieties and at least one of R₂ and R₃is a mono or poly-unsaturated hydrocarbon radical; or mixtures thereof.

In a preferred embodiment, the lubricant composition consistingessentially of between about 50% and about 75% by volume of a filmforming lubricant consisting essentially of unsaturated fatty acid(s)having between about 18 and about 24 carbon atoms and between one andthree carboxylic acid moieties;

between 20% and about 45% by weight of a suspension agent comprising ametal salt or metal base reactable with at least one carboxylic acidmoiety in the unsaturated fatty acid, wherein the metal is a Group Imetal, a Group II metal, or mixture thereof, wherein the amount ofsuspension agent is sufficient to provide at least a 50% overbasedcomposition; and

between about 15 and about 30 pounds of a polymeric particulate thatfunctions as a mechanical lubricant per barrel of lubricant composition,wherein the polymeric particulate consists of polymeric beads having asize between 40 mesh to 100 mesh, the beads comprising a cross-linkedpolymer or copolymer of styrene, divinylbenzene, PVC/vinylacetate,vinylidene chloride/acrylonitrile, methylmethacrylate/ethylacrylate, orstyrene/divinylbenzene; wherein said lubricant composition is blended toform a substantially homogenous composition.

DESCRIPTION OF EMBODIMENTS OF THE INVENTION

The present invention is a lubricant that has the combined properties ofa liquid film forming lubricant and a mechanical lubricant. The combinedlubricant of the present invention includes the following threecomponents:

a film forming liquid lubricant, e.g., one or more tall oil fatty acidcompounds;

a suspension agent, e.g., an alkali metal, alkali earth metal, or metaloxide or carbonyl; and

a particulate mechanical lubricant, e.g., a polymeric solidadvantageously preformed into discrete particles.

In one embodiment, the lubricant composition comprises:

between about 40% and about 80%, preferably between about 50% and about75%, more preferably from about 60% to about 70% by volume of a filmforming liquid lubricant, e.g., one or more tall oil fatty acidcompounds;

between about 10% and 50% for example between about 20% and about 45%,or between about 30% and about 40% by weight, of a suspension agent,e.g., an alkali metal, alkali earth metal, or metal compound, whereinthe metal ratio is at least about 1.5, for example between about 2 and12, alternately between about 3 and 6; and

between about 10 and about 50, for example between 10 and about 35, oralternately between about 15 to about 20 pounds per barrel of lubricantof a polymeric particulate mechanical lubricant, e.g., polystyrene orpolydivinylbenzenestyrene beads.

The lubricant composition can optionally contain any of the following:

promoters useful for forming the overbased film forminglubricant/suspension agent composition, so long as the amount ofpromoters is less than about 2% by weight, for example between 0.1% and1.9% by weight;

between about 0 and about 2%, for example between about 0.1% and 1%,each of resin acids, unsaponifiables, and saturated fatty acids andtheir isomers; and

between about 0 and about 5%, for example between about 0.1% and 4%, ofadditional inorganic particulate lubricant material comprising graphite,molybdenum disulphide, lead oxide, lime, talc, bentonite, or particlesof aluminum, copper, lead, zinc, glass, or ceramic.

In a preferred embodiment the lubricant composition is substantiallyfree of promoters. In a preferred embodiment the lubricant compositionis substantially free of resin acids, unsaponifiables, and saturatedfatty acids and their isomers. In a preferred embodiment the lubricantcomposition is substantially free of inorganic particulate lubricantmaterial. In each case substantially free means less than 0.3% by weightof the component(s) in the lubricant composition. In another embodimentthe lubricant composition comprises between 0.1% and 4% of inorganicparticulate lubricant material selected from graphite, molybdenumdisulphide, glass, or ceramic.

Each component will now be further described.

Generally, the amount of film forming liquid lubricant is between about50 and 75 V/V %, preferably from about 60 to about 70 V/V %, based onthe volume of the lubricant composition. The film forming liquidlubricant comprises or consists essentially of one or more of:

1) a fatty acid having between about 16 and about 26 carbon atoms,preferably having between about 18 and about 20 carbon atoms, andbetween one and three carboxylic acid moieties per molecule, preferablyhaving one carboxylic acid moiety per molecule, and preferably havingbetween 1 and 3 carbon-carbon double bonds; and

2) a triglyceride with the fatty acids having from about 16 to about 26carbon atoms and at least one double bond, but no more than three doublebonds for at least 90% of the fatty acids. All isomers of these areincluded, but straight chain groups are preferred.

In one preferred embodiment, the film forming liquid lubricant comprisesat least 50% by weight of, or consists essentially of, one or more talloil fatty acids, having for example from about 18 to about 20 carbonatoms with the majority of fatty acids having one double bond. Inanother embodiment, the film forming liquid lubricant comprises at least50% by weight of, or consists essentially of, one or more of linoleicacid, abietic acid, linolenic acid, palmitoleic acid, oleic acid andricinoleic acid. The film forming lubricant should be ecologicallyacceptable and accordingly in the preferred embodiment should have noaromatic constituents. Straight-chain and/or branched unsaturated,particularly olefin mono- and/or poly-unsaturated, fatty are thepreferred compounds. In a preferred embodiment, the film forming liquidlubricant comprises at least 50% by weight of, or consists essentiallyof, one or more tall oil fatty acids, e.g., a light-yellow oily liquidwhich is a mixture of high molecular unsaturated organic acids sucholeic, linoleic, linolenic acids and their isomers. In another preferredembodiment, the film forming liquid lubricant comprises at least 50% byweight of, or consists essentially of, one or more of linoleic acid,linolenic acid, and oleic acid. A normal sunflower oil has from 20-40percent oleic acid and from 50-70 percent linoleic acid. In oneembodiment, the film forming liquid lubricant is comprised of EZESlide™,a tall oil fatty acid compound, marketed by Sun Drilling Products, Inc.

Film forming lubricants typically are commercially available in mixtureswith certain contaminants, in particular resin acids, unsaponifiables,and saturated fatty acids and their isomers. The preferred lubricantcompositions are substantially free of these components. Bysubstantially free it is meant less than 2%, preferably less than 1%, ofeach of the three general components. Resin acids are believed to causeundesired thickening. Unsaponifiables are a general term for organiccontaminants that are typically undefined. Saturated fatty acids areused in many prior art lubricant formulations, but applicants have foundthat when present, they have a tendency to react with low-salinitybrines to form undesirable foams.

The lubricant composition typically comprises between about 20% andabout 45%, for example between about 30% and about 40% by weight, of asuspension agent. The suspension agent generally comprises or consistsessentially of one or more metal compounds described infra. The metalcompounds useful in making the suspension agent are generally any one ormore of Group I and/or Group II metal compounds (CAS version of thePeriodic Table of the Elements). The Group I metals of the metalcompound include alkali metals (sodium, potassium, lithium, etc.) aswell as Group IB metals such as copper. The preferred Group I metals aresodium, potassium, and lithium, more preferably sodium and potassium,and most preferably sodium. The Group II metals include the alkalineearth metals (magnesium, calcium, barium, etc.) as well as the Group IIBmetals such as zinc or cadmium. The preferred Group II metals aremagnesium, calcium, barium, or zinc, more preferably magnesium orcalcium, and most preferably calcium. Generally the metal compounds areadmixed into the film forming lubricant composition as metal salts, andare preferably metal bases. In one embodiment at least half of theequivalents of the suspension agent are Group II salts. In a preferredembodiment at least half, preferably at least 80%, by weight ofsuspension agent is an alkaline earth metal compound, e.g., calcium. Ineach of the above embodiments, the anionic portion of the salt can beany counterion, e.g., a hydroxyl, oxide, carbonyl, carbonate, borate,nitrate, etc. Preferably the anionic portion is a base, e.g., ahydroxyl, a carbonyl, a carbonate, or mixture thereof. In a preferredembodiment, the suspension agent comprises metal-base salts in an amountsuch that the basic equivalents of base anions are at least 1.5 timesthe acidic equivalents of film forming liquid lubricant.

Alternately or additionally, the suspension agent can comprise orconsist essentially of one or more liquid coating amines. Representativeliquid coating amines are described in for example U.S. Pat. No.5,320,768, the disclosure of which is incorporated herein by referencethereto, describing an amine is represented by the formula R₁—N—(R)₂,where each R group is a C2 to C5 alkylene and the R1 group is a C3 toC24 saturated or unsaturated aliphatic group or two saturated orunsaturated aliphatic group with an oxygen therebetween, wherein theamine has between ten and thirty carbon atoms. Another useful liquidcoating amine is a basic amine compound of marked oleophilic nature andat most limited water solubility, which is capable of forming salts withcarboxylic acids, as disclosed in U.S. Pat. No. 5,348,938, thedisclosure of which is incorporated herein by reference thereto. Inparticular, optionally olefin-unsaturated aliphatic, cycloaliphaticand/or heterocyclic oleophilic basic amine compounds which contain oneor more N-groups capable of forming salts with carboxylic acids areincluded, for example a basic amine compound having at least onelong-chain hydrocarbon radical with 10 to 24 carbon atoms, which can beolefin mono- or poly-unsaturated. The filming amine can be a corrosioninhibitor which plates out or coats metal surfaces, such as Arcor 233available from Baker Performance Chemicals, Dayton, Tex.

If the composition is substantially free of metal salt suspensionagents, it is preferred that the moles of amine are at least 1.5 times,more preferably at least 2 times, the moles of tall fatty acids in theliquid film forming lubricant.

In preferred embodiments of the invention, where liquid coating aminesare included in the suspension agent, the suspension agent furthercomprises metal-base salts in an amount such that the basic equivalentsof base anions are at least 1.5 times the acidic equivalents of filmforming liquid lubricant.

The film forming agent and the suspension agent can be reacted to form agrease as is known in the art. The film-forming lubricant and thesuspension agent should be present in an amount to give an over-basedcomposition. Over-basing, also referred to as superbasing orhyperbasing, is a means for supplying a large quantity of basic materialin a form which is soluble or dispersible in the fatty acid. Overbasedproducts have been long used in lubricant technology to providedetergent additives. Overbased materials are often single phase,homogeneous systems characterized by a metal content in excess of thatwhich would be present according to the stoichiometry of the metal andthe particular acidic organic compound reacted with the metal. Theamount of excess metal is commonly expressed in terms of metal ratio.The term “metal ratio” is the ratio of the total equivalents of themetal to the equivalents of the acidic organic compound. A neutral metalsalt, e.g., a composition having about 12 parts calcium hydroxide per 88parts of linoleic acid, by weight, has a metal ratio of one. Acomposition having 1.5 times as much metal as present in a neutral saltwill have a ratio of 1.5. For example, a composition having 14 partscalcium hydroxide per 86 parts of linoleic acid, by weight, will have ametal ratio of about 1.2. A composition having about 17 parts calciumhydroxide per 83 parts of linoleic acid, by weight, has a metal ratio of1.5. It is preferred that the metal ratio of the suspension agent tofilm forming liquid lubricant is greater than about 1.2. The ratio ofequivalents of suspension agent to film forming liquid lubricant of thepresent invention in one embodiment has a metal ratio of greater than1.5, e.g., from 2 to 12, for example 3 to 6 or alternatively 3.5 to 5.

Promoters are chemicals which are sometimes employed to facilitate theincorporation of suspension agent metal into the basic metalcompositions. Among the chemicals useful as promoters are water,ammonium hydroxide, organic acids of up to about 8 carbon atoms, nitricacid, hydrochloric acid, metal complexing agents such as alkylsalicylaldoxime, and alkali metal hydroxides such as lithium hydroxide,sodium hydroxide and potassium hydroxide, and mono- and polyhydricalcohols of up to about 30 carbon atoms. Examples of the alcoholsinclude methanol, ethanol, isopropyl alcohol, butyl alcohol, isobutylalcohol, dodecanol, behenyl alcohol, ethylene glycol, monomethylether ofethylene glycol, hexamethylene glycol, glycerol, pentaerythritol, benzylalcohol, phenylethyl alcohol, aminoethanol, cinnamyl alcohol, allylalcohol, and the like. Especially useful are the monohydric alcoholshaving up to about 10 carbon atoms and mixtures of methanol with highermonohydric alcohols. It is characteristic of promoters that they arenormally employed in low quantities, normally at less than 1-2% byweight of the reaction mixture for promoters which are not laterremoved. Thus they do not normally constitute an appreciable portion ofthe acid functionality of the composition, but serve rather a role moreas a catalyst for the overbasing process.

The lubricant composition advantageously comprises, per barrel oflubricant composition, between 10 and about 35 pounds per barrel(“ppb”), preferably between about 15 to about 20 ppb, of a polymericparticulate mechanical lubricant. The particulate mechanical lubricantis beneficially a polymeric solid preformed into discrete particles(beads). The size of the beads can vary over a substantial range such asfrom 10 to 800 mesh (Tyler standard screen size), for example from 20 to400 mesh. A preferred particulate size for the polymeric beads is 40mesh to 100 mesh, and more preferably is 60 mesh to 80 mesh. In apreferred embodiment, the particles or beads have a weight averageparticle diameter between about 220 and about 280 microns, with lessthan 30% by weight having a diameter less than 150 microns and less than5% by weight greater than about 350 microns. Over-sized particles canplug close tolerances found in some coiled tubing applications, whiletoo small a particle provides insufficient material between a tubing ordrilling pipe and an annulus, for example, to adequately lubricate thetubing or drilling pipe.

In one embodiment the particulate mechanical lubricant comprises beadsof one or more of crosslinked polymers, e.g., polymers of styrenes,PVC/vinylacetate, vinylidene chloride/acrylonitrile, methylmethacrylateand ethylacrylate, and styrene and divinylbenzene copolymers, asdisclosed for example in U.S. Pat. Nos. 4,063,603; 4,172,031; 4,269,279;4,384,095 and 4,427,793, the disclosures of which are incorporated byreference. A preferred particulate mechanical lubricant is beads formedof polymerized divinyl benzene, styrene, divinyl benzene/styrene,polystyrene crosslinked with divinyl benzene, or mixtures orcombinations thereof. In a preferred embodiment the first copolymercompound comprises Lubra-Glide® Beads CE copolymer, having a specificgravity of about 1.06 to about 1.1, which are commercially availablefrom Sun Drilling Products, Inc. Other copolymer lead products are thosedisclosed in co-owned U.S. Pat. No. 6,541,599 and 6,348,629 thedisclosure of which is incorporated herein by reference.

The components should be blended to form a substantially homogenouslubricant composition, e.g., a lubricant composition where misciblecomponents are well mixed and where immiscible solid components aresubstantially evenly distributed in the lubricant composition.

The lubricant composition is particularly useful in oil well operations,including drilling, running tubing or pipe, and other activities whereextreme pressures can be generated. The lubricant composition can beapplied by for example admixing between 1% and 5%, for example betweenabout 2% and 4% by volume, into drilling mud. The lubricant compositionwill plate out from the mud onto the metal surfaces, in strongpreference to un-desired plating out for example on clay, weightingagents, and sand. The greasy fraction will hold the particulatelubricants in place.

Minor amounts of biocides may be added to the lubricant composition ifappropriate for the end use.

The lubricant composition should be ecologically acceptable andaccordingly in the preferred embodiment should have no aromaticconstituents and no environmentally detrimental metals. A compositioncomprising tall fatty acids, calcium hydroxide, andpolystyrene-divinylbenzene beeads has an LC50 above 750000 ppm at 2% byvolume in “generic 7 mud”. The concentration of the chemical in air thatkills 50% of test animals in a given time (usually four hours) is theLC50 value, and the appropriate tests for various systems are known tothose of skill in the art.

The lubricant has a boiling point of about 250° F. to 450° F., forexample, 400-450. Preferred embodiments of the lubricant composition arethermally stable and useful at downhole temperatures above 250° F.

EXAMPLE

An aqueous lubricant having about 65% by volume of EZESlide™, a tall oilfatty acid compound marketed by Sun Drilling Products, Inc, about 33% byvolume of calcium hydroxide, and about about 2% by volume LUBRAGLIDE CECopolymer™ beads was blended to form an overbased, substantially uniformcomposition. This material was found to have an LC50 above 750000 ppm at2% by volume in generic 7 mud. This material was added in an amountbetween about 2% to 3% into a drilling mud, and the lubricantcomposition provided excellent improvements in lubricity down-hole asexhibited by reduced torque.

As used herein, unless otherwise specifically described, the mention ofa single component, for example the term “film forming lubricant”,encompasses both a singular compound and a plurality of compounds thateach meet the requirements of the definition of the term.

Although the present invention is described with reference to certainpreferred embodiments, it is apparent that modification and variationsthereof may be made by those skilled in the art without departing fromthe spirit and scope of this invention as defined by the appendedclaims. In particular, it will be clear to those skilled in the art thatthe present invention may be embodied in other specific forms,structures, arrangements, proportions, and with other elements,materials, and components, without departing from the spirit oressential characteristics thereof. One skilled in the art willappreciate that the invention may be used with many modifications ofmaterials, methods, and components otherwise used in the practice of theinvention, which are particularly adapted to specific substrates andoperative requirements without departing from the principles of thepresent invention. The presently disclosed embodiments are therefore tobe considered in all respects as illustrative and not restrictive, thescope of the invention being indicated by the appended claims, and notlimited to the foregoing description.

1. A lubricant composition comprising: between about 40% and about 80%by volume of a film forming lubricant consisting essentially ofunsaturated fatty acid(s) having between 16 and 26 carbon atoms andbetween one and three carboxylic acid moieties, or triglyceride(s)having from 16 to 26 carbon atoms and at least one double bond, ormixture thereof; at least about 20% by weight of a suspension agentcomprising: a metal compound reactable with at least one carboxylic acidmoiety in the unsaturated fatty acid, wherein the metal is a Group Imetal, a Group II metal, or mixture thereof; a film-forming amineR₁—N—(R)₂, where: each R is independently an H or a C₂ to C₅ alkylene,and R₁ is a C₃ to C₂₄ saturated or unsaturated aliphatic group or twosaturated or unsaturated aliphatic groups with an oxygen therebetween,wherein the amine has between ten and thirty carbon atoms; each R isindependently an H, a C₂ to C₅ alkylene, or a C₁ to C₅ alkyl or alkanol,and R₁ contains between 10 and 24 carbon atoms and is a C₁₀ to C24 mono-or poly-unsaturated hydrocarbon radical or a group R₂—O—R₃; wherein R₂and R₃ are hydrocarbon moieties and at least one of R₂ and R₃ is a monoor poly-unsaturated hydrocarbon radical; or mixtures thereof, whereinthe amount of suspension agent is sufficient to provide at least a 50%overbased composition; and between about 10 and about 50 pounds ofpolymeric beads per barrel of lubricant composition, wherein saidlubricant composition is blended to form a substantially homogenouscomposition.
 2. The lubricant composition of claim 1, wherein thelubricant composition comprises: between about 50% and about 75% byvolume of tall oil fatty acids; between 20% and about 45% by weight ofthe suspension agent; and between about 10 and about 35 pounds of thepolymeric beads per barrel of lubricant composition.
 3. The lubricantcomposition of claim 1, wherein the lubricant composition consistsessentially of: between about 50% and 80% by volume of tall oil fattyacids; between 20% and about 45% by weight of the suspension agent,wherein the suspension agent comprises the metal compound, and whereinthe metal is a Group I metal, a Group II metal, or mixture thereof, andbetween about 10 and about 35 pounds of the polymeric beads per barrelof lubricant composition.
 4. The lubricant composition of claim 1,wherein the lubricant composition comprises: between about 60% and about70% by volume of unsaturated fatty acid(s) having between about 18 andabout 22 carbon atoms and between one and three carboxylic acidmoieties; between 30% and about 40% by weight of the suspension agent,wherein the suspension agent comprises the metal compound, and whereinthe metal is a Group I metal, a Group II metal, or mixture thereof; andbetween about 15 and about 20 pounds of the polymeric beads per barrelof lubricant composition.
 5. The lubricant composition of claim 1,wherein the lubricant composition comprises: between about 60% and about70% by volume of tall oil fatty acids; between 30% and about 40% byweight of the suspension agent, wherein the suspension agent comprises ametal base compound, and wherein the metal is a Group I metal, a GroupII metal, or mixture thereof, and between about 15 and about 20 poundsof a polymeric beads per barrel of lubricant composition.
 6. Thelubricant composition of claim 1, wherein the lubricant compositioncomprises: between about 60% and about 70% by volume of the unsaturatedfatty acid(s) having between about 16 and about 26 carbon atoms andbetween one and three carboxylic acid moieties, the triglyceride(s)having from about 16 to about 26 carbon atoms and at least one doublebond, or mixture thereof; between 30% and about 40% by weight of thesuspension agent, wherein the suspension agent comprises the metalcompound, and wherein the metal is a Group I metal, a Group II metal, ormixture thereof; and between about 10 and about 35 pounds of a polymericbeads per barrel of lubricant composition.
 7. The lubricant compositionof claim 1, wherein the lubricant composition consists essentially of:between about 60% and about 75% by volume of the unsaturated fattyacid(s) having between about 18 and about 22 carbon atoms and betweenone and three carboxylic acid moieties; between 30% and about 40% byweight of the suspension agent, wherein the suspension agent comprisesthe metal compound, and wherein the metal is a Group I metal, a Group IImetal, or mixture thereof; and between about 15 and about 20 pounds ofthe polymeric beads per barrel of lubricant composition.
 8. Thelubricant composition of claim 1, wherein the film forming lubricantcomprises at least 50% by weight of one or more tall oil fatty acids. 9.The lubricant composition of claim 1, wherein the suspension agentconsists essentially of a metal salt, wherein the metal is sodium,potassium, and lithium, magnesium, calcium, barium, or mixture thereof.10. The lubricant composition of claim 9, wherein the metal ratio isbetween about 2 and
 12. 11. The lubricant composition of claim 1,wherein the polymeric beads have a size between 40 mesh to 100 mesh, thebeads comprising a cross-linked polymer or copolymer of styrene,divinylbenzene, PVC/vinylacetate, vinylidene chloride/acrylonitrile,methylmethacrylate/ethylacrylate, or styrene/divinylbenzene.
 12. Thelubricant composition of claim 1, wherein the polymeric beads have asize between 60 mesh to 80 mesh, the beads comprising a cross-linkedpolymerized divinyl benzene, styrene, divinyl benzene/styrene,polystyrene crosslinked with divinyl benzene, or mixtures orcombinations thereof.
 13. The lubricant composition of claim 1, whereinthe polymeric beads have a weight average particle diameter betweenabout 220 and about 280 microns, with less than 30% by weight having adiameter less than 150 microns and less than 5% by weight having adiameter greater than about 350 microns.
 14. The lubricant compositionof claim 1, wherein the lubricant composition comprises less than about2% by weight of each of: promoters useful for forming the overbased filmforming lubricant/suspension agent composition; resin acids;unsaponifiables; and saturated fatty acids and their isomers.
 15. Thelubricant composition of claim 14, wherein the lubricant compositioncomprises less than about 5% by weight total of promoters useful forforming the overbased film forming lubricant/suspension agentcomposition, resin acids, unsaponifiables, and saturated fatty acids.16. The lubricant composition of claim 1, wherein the lubricantcomposition comprises less than about 1% by weight of each of: promotersuseful for forming the overbased film forming lubricant/suspension agentcomposition; resin acids; unsaponifiables; and saturated fatty acids andtheir isomers.
 17. The lubricant composition of claim 1, furthercomprising between about 0.1% and about 5%, of inorganic particulatelubricant.
 18. The lubricant composition of claim 17, wherein theinorganic particulate lubricant comprises graphite, molybdenumdisulphide, lead oxide, or particles of aluminum, copper, lead, zinc,glass, or ceramic.
 19. The lubricant composition of claim 17, whereinthe inorganic particulate lubricant comprises graphite, molybdenumdisulphide, glass, or ceramic.
 20. The lubricant composition of claim 1,wherein the film forming lubricant comprises at least 50% by weight ofunsaturated fatty acids having between 18 and about 20 carbon atoms. 21.The lubricant composition of claim 1, wherein the lubricant compositionis substantially free of aromatics, cadmium, and lead.
 22. The lubricantcomposition of claim 1, wherein at least half of the equivalents of thesuspension agent are salts or bases of Group II metals.
 23. Thelubricant composition of claim 1, wherein at least half by weight ofsuspension agent is an alkaline earth metal base where the counter-ionis a hydroxyl, a carbonyl, a carbonate, or mixture thereof.
 24. A methodof lubricating a pipe in a wellbore, the method comprising: addingbetween about 1% and about 5% by volume of the lubricant composition ofclaim 1 to a treating fluid; and circulating the fluid containing thelubricant into the well to place the lubricant at the desired depth. 25.The method of claim 25, wherein the treating fluid is an aqueous-baseddrilling mud and the quantity of lubricant composition added is betweenabout 2% and about 3% by volume.
 26. The method of claim 25, wherein thetreating fluid is an oil-based drilling mud and the quantity oflubricant composition added is between about 2% and about 3% by volume.27. A lubricant composition comprising: between about 50% and about 80%by volume of a film forming lubricant consisting essentially ofunsaturated fatty acid(s) having between about 18 and about 24 carbonatoms and between one and three carboxylic acid moieties; between 20%and about 45% by weight of a suspension agent comprising a metal salt ormetal base reactable with at least one carboxylic acid moiety in theunsaturated fatty acid, wherein the metal is a Group I metal, a Group IImetal, or mixture thereof, wherein the amount of suspension agent issufficient to provide at least a 50% overbased composition; and betweenabout 10 and about 35 pounds of a polymeric particulate that functionsas a mechanical lubricant per barrel of lubricant composition, whereinthe polymeric particulate consists of polymeric beads having a sizebetween 40 mesh to 100 mesh, the beads comprising a cross-linked polymeror copolymer of styrene, divinylbenzene, PVC/vinylacetate, vinylidenechloride/acrylonitrile, methylmethacrylate/ethylacrylate, orstyrene/divinylbenzene; wherein said lubricant composition is blended toform a substantially homogenous composition.
 28. The lubricantcomposition of claim 28, further comprising between 5% and 20% by weightof a film-forming amine R₁—N—(R)₂, where: each R is independently an Hor a C₂ to C₅ alkylene, and R₁ is a C₃ to C₂₄ saturated or unsaturatedaliphatic group or two saturated or unsaturated aliphatic groups with anoxygen therebetween, wherein the amine has between ten and thirty carbonatoms; each R is independently an H, a C₂ to C₅ alkylene, or a C₁ to C₅alkyl or alkanol, and R₁ contains between 10 and 24 carbon atoms and isa C₁₀ to C₂₄ mono- or poly-unsaturated hydrocarbon radical or a groupR₂—O—R₃; wherein R₂ and R₃ are hydrocarbon moieties and at least one ofR₂ and R₃ is a mono or poly-unsaturated hydrocarbon radical; or mixturesthereof.
 29. The lubricant composition of claim 28 consistingessentially of between about 50% and about 75% by volume of a filmforming lubricant consisting essentially of unsaturated fatty acid(s)having between about 18 and about 24 carbon atoms and between one andthree carboxylic acid moieties; between 20% and about 45% by weight of asuspension agent comprising a metal salt or metal base reactable with atleast one carboxylic acid moiety in the unsaturated fatty acid, whereinthe metal is a Group I metal, a Group II metal, or mixture thereof,wherein the amount of suspension agent is sufficient to provide at leasta 50% overbased composition; and between about 15 and about 30 pounds ofa polymeric particulate that functions as a mechanical lubricant perbarrel of lubricant composition, wherein the polymeric particulateconsists of polymeric beads having a size between 40 mesh to 100 mesh,the beads comprising a cross-linked polymer or copolymer of styrene,divinylbenzene, PVC/vinylacetate, vinylidene chloride/acrylonitrile,methylmethacrylate/ethylacrylate, or styrene/divinylbenzene; whereinsaid lubricant composition is blended to form a substantially homogenouscomposition.